The structures of bis[(
R)-(+)-1-phenylethylammonium] (2
R,3
R)-(−)-2,3-di-
p-toluoyloxybutanedioate methanol disolvate monohydrate, 2C
8H
12N
+·C
20H
16O
82−·2CH
4O·H
2O, (I), and bis(benzylammonium) (2
R,3
R)-(−)-2,3-di-
p-toluoyloxybutanedioate dihydrate, 2C
7H
10N
+·C
20H
16O
82−·2H
2O, (II), exhibit extensive hydrogen bonding, with (N—)H
O and (O—)H
O distances in the ranges 2.716 (2)–2.929 (3) and 2.687 (2)–2.767 (2) Å, respectively, in (I), and 2.673 (2)–2.888 (2) and 2.785 (2)–2.931 (2) Å, respectively, in (II). The amine groups are protonated and the carboxylate groups of the tartrate anions are fully deprotonated. The conformation of the toluoyltartrate anion and its molecular parameters are similar in both structures.
Supporting information
CCDC references: 612466; 612467
Tartaric acid and the appropriate amine guest, in a mole ratio of 1:2, were dissolved in warm wet methanol solvent (Temperature? Ratio of alcohol and water?). The resultant solutions were allowed to stand at room temperature. Colourless crystals of (I) and (II) appeared after a few days from their respective mother liquor.
Both structure solutions and refinements proceeded routinely. Friedel equivalents were merged in the final refinement cycles. All non-H atoms were refined anisotropically. The functional H atoms of the methanol hydroxyl group, the water hydroxyl group and the amine cation NH3+ were located in a difference electron-density map and refined independently with simple bond-length constraints (Restraints?). [Please give details of restraints used and ranges of refined distances.] The remaining H atoms were placed in idealized positions in a riding model, with C—H = 0.95–1.00 Å, and refined with Uiso(H) = 1.2–1.5Ueq(C).
For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997), X-SEED (Barbour, 2001) and POVRAY (Cason, Year?); software used to prepare material for publication: SHELXL97.
(I) bis[(
R)-(+)-1-phenylethylammonium] (2
R,3
R)-(-)-2,3-di-
p-toluoyloxybutanedioate methanol disolvate monohydrate
top
Crystal data top
2C8H12N+·C20H16O82−·2CH4O·H2O | F(000) = 760 |
Mr = 710.80 | Dx = 1.242 Mg m−3 |
Monoclinic, P21 | Melting point: not measured K |
Hall symbol: P 2yb | Mo Kα radiation, λ = 0.71073 Å |
a = 10.9366 (1) Å | Cell parameters from 43385 reflections |
b = 8.0785 (1) Å | θ = 3.8–26.4° |
c = 22.0995 (2) Å | µ = 0.09 mm−1 |
β = 103.324 (1)° | T = 113 K |
V = 1899.96 (3) Å3 | Prism, colourless |
Z = 2 | 0.40 × 0.40 × 0.35 mm |
Data collection top
Nonius Kappa CCD area-detector diffractometer | 3969 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.009 |
Graphite monochromator | θmax = 26.4°, θmin = 4.2° |
1.2° ϕ scans and ω scans | h = −13→13 |
7708 measured reflections | k = −10→10 |
7708 independent reflections | l = −27→27 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.095 | w = 1/[σ2(Fo2) + (0.0488P)2 + 0.6269P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.001 |
7708 reflections | Δρmax = 0.38 e Å−3 |
502 parameters | Δρmin = −0.26 e Å−3 |
11 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.035 (3) |
Crystal data top
2C8H12N+·C20H16O82−·2CH4O·H2O | V = 1899.96 (3) Å3 |
Mr = 710.80 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.9366 (1) Å | µ = 0.09 mm−1 |
b = 8.0785 (1) Å | T = 113 K |
c = 22.0995 (2) Å | 0.40 × 0.40 × 0.35 mm |
β = 103.324 (1)° | |
Data collection top
Nonius Kappa CCD area-detector diffractometer | 3969 reflections with I > 2σ(I) |
7708 measured reflections | Rint = 0.009 |
7708 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 11 restraints |
wR(F2) = 0.095 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.38 e Å−3 |
7708 reflections | Δρmin = −0.26 e Å−3 |
502 parameters | |
Special details top
Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 35 mm; combination of ϕ and ω scans of 1.2°, 40 s per °, 2 iterations. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.43263 (16) | 0.6310 (2) | 0.33632 (8) | 0.0251 (4) | |
O2 | 0.49430 (15) | 0.7944 (2) | 0.41991 (7) | 0.0232 (3) | |
O3 | 0.57209 (15) | 1.2349 (2) | 0.28196 (7) | 0.0231 (3) | |
O4 | 0.64452 (14) | 1.0498 (2) | 0.22387 (7) | 0.0222 (3) | |
O5 | 0.40860 (13) | 0.8900 (2) | 0.25667 (6) | 0.0188 (3) | |
O6 | 0.22347 (14) | 0.9170 (2) | 0.28353 (7) | 0.0258 (4) | |
O7 | 0.67107 (13) | 0.81505 (19) | 0.31307 (7) | 0.0182 (3) | |
O8 | 0.84887 (14) | 0.9665 (2) | 0.33804 (8) | 0.0239 (4) | |
O41 | 0.8126 (2) | 1.0909 (3) | 0.14869 (12) | 0.0573 (7) | |
O51 | 0.62194 (16) | 0.7457 (2) | 0.16569 (8) | 0.0304 (4)* | |
O61 | 0.44125 (19) | 0.3114 (2) | 0.37065 (9) | 0.0322 (4) | |
N21 | 0.42734 (19) | 0.1116 (3) | 0.46770 (9) | 0.0235 (4) | |
N31 | 0.48447 (18) | 0.5304 (3) | 0.22150 (9) | 0.0226 (4) | |
C1 | 0.4638 (2) | 0.7666 (3) | 0.36273 (10) | 0.0187 (4) | |
C2 | 0.47025 (19) | 0.9173 (3) | 0.32111 (9) | 0.0177 (4) | |
H2 | 0.4291 | 1.0134 | 0.3370 | 0.021* | |
C3 | 0.60531 (19) | 0.9638 (3) | 0.32204 (10) | 0.0175 (4) | |
H3 | 0.6452 | 1.0122 | 0.3635 | 0.021* | |
C4 | 0.60896 (18) | 1.0931 (3) | 0.27086 (10) | 0.0180 (4) | |
C5 | 0.28199 (19) | 0.9076 (3) | 0.24356 (10) | 0.0200 (4) | |
C6 | 0.2279 (2) | 0.9206 (3) | 0.17572 (10) | 0.0226 (5) | |
C7 | 0.3012 (2) | 0.9489 (3) | 0.13326 (11) | 0.0267 (5) | |
H7 | 0.3902 | 0.9517 | 0.1469 | 0.032* | |
C8 | 0.2453 (2) | 0.9732 (4) | 0.07107 (12) | 0.0338 (6) | |
H8 | 0.2963 | 0.9927 | 0.0423 | 0.041* | |
C9 | 0.1150 (3) | 0.9694 (4) | 0.05017 (12) | 0.0382 (6) | |
C10 | 0.0428 (2) | 0.9387 (4) | 0.09291 (13) | 0.0405 (7) | |
H10 | −0.0461 | 0.9337 | 0.0791 | 0.049* | |
C11 | 0.0971 (2) | 0.9153 (4) | 0.15494 (12) | 0.0325 (6) | |
H11 | 0.0459 | 0.8957 | 0.1836 | 0.039* | |
C12 | 0.0539 (3) | 1.0028 (6) | −0.01719 (14) | 0.0586 (10) | |
H12C | −0.0030 | 0.9115 | −0.0338 | 0.088* | |
H12B | 0.1189 | 1.0122 | −0.0410 | 0.088* | |
H12A | 0.0062 | 1.1064 | −0.0205 | 0.088* | |
C13 | 0.79791 (19) | 0.8364 (3) | 0.32204 (10) | 0.0183 (4) | |
C14 | 0.8628 (2) | 0.6832 (3) | 0.31045 (10) | 0.0183 (4) | |
C15 | 0.9850 (2) | 0.6969 (3) | 0.30298 (11) | 0.0231 (5) | |
H15 | 1.0220 | 0.8031 | 0.3023 | 0.028* | |
C16 | 1.0530 (2) | 0.5564 (3) | 0.29654 (12) | 0.0267 (5) | |
H16 | 1.1371 | 0.5672 | 0.2922 | 0.032* | |
C17 | 1.0006 (2) | 0.3997 (3) | 0.29625 (11) | 0.0256 (5) | |
C18 | 0.8757 (2) | 0.3874 (3) | 0.30105 (12) | 0.0271 (5) | |
H18 | 0.8370 | 0.2816 | 0.2990 | 0.033* | |
C19 | 0.8078 (2) | 0.5269 (3) | 0.30871 (11) | 0.0225 (5) | |
H19 | 0.7236 | 0.5164 | 0.3128 | 0.027* | |
C20 | 1.0744 (3) | 0.2453 (4) | 0.29061 (14) | 0.0344 (6) | |
H20C | 1.0660 | 0.2189 | 0.2466 | 0.052* | |
H20A | 1.0420 | 0.1531 | 0.3111 | 0.052* | |
H20B | 1.1631 | 0.2635 | 0.3105 | 0.052* | |
C21 | 0.2857 (2) | 0.1047 (3) | 0.44991 (11) | 0.0267 (5) | |
H21 | 0.2597 | 0.0928 | 0.4037 | 0.032* | |
C22 | 0.2375 (2) | −0.0442 (3) | 0.47825 (11) | 0.0272 (5) | |
C23 | 0.1547 (4) | −0.1501 (6) | 0.44080 (15) | 0.0765 (15) | |
H23 | 0.1307 | −0.1297 | 0.3973 | 0.092* | |
C24 | 0.1055 (4) | −0.2862 (6) | 0.46522 (18) | 0.0852 (17) | |
H24 | 0.0483 | −0.3576 | 0.4385 | 0.102* | |
C25 | 0.1391 (3) | −0.3182 (4) | 0.52799 (13) | 0.0415 (7) | |
H25 | 0.1044 | −0.4098 | 0.5452 | 0.050* | |
C26 | 0.2244 (3) | −0.2145 (4) | 0.56548 (12) | 0.0371 (6) | |
H26 | 0.2509 | −0.2374 | 0.6087 | 0.045* | |
C27 | 0.2720 (3) | −0.0779 (4) | 0.54123 (11) | 0.0343 (6) | |
H27 | 0.3289 | −0.0064 | 0.5680 | 0.041* | |
C28 | 0.2339 (3) | 0.2681 (4) | 0.46704 (14) | 0.0374 (6) | |
H28A | 0.1422 | 0.2686 | 0.4523 | 0.056* | |
H28C | 0.2697 | 0.3593 | 0.4475 | 0.056* | |
H28B | 0.2562 | 0.2818 | 0.5123 | 0.056* | |
C31 | 0.3672 (2) | 0.5026 (3) | 0.17225 (11) | 0.0265 (5) | |
H31 | 0.3231 | 0.6112 | 0.1627 | 0.032* | |
C32 | 0.3971 (2) | 0.4375 (3) | 0.11329 (10) | 0.0239 (5) | |
C33 | 0.3242 (3) | 0.4885 (4) | 0.05607 (12) | 0.0346 (6) | |
H33 | 0.2596 | 0.5681 | 0.0546 | 0.042* | |
C34 | 0.3454 (3) | 0.4238 (4) | 0.00136 (12) | 0.0425 (7) | |
H34 | 0.2940 | 0.4573 | −0.0375 | 0.051* | |
C35 | 0.4403 (3) | 0.3116 (5) | 0.00291 (12) | 0.0444 (8) | |
H35 | 0.4563 | 0.2699 | −0.0347 | 0.053* | |
C36 | 0.5126 (3) | 0.2595 (5) | 0.05951 (13) | 0.0439 (7) | |
H36 | 0.5778 | 0.1811 | 0.0607 | 0.053* | |
C37 | 0.4904 (2) | 0.3210 (4) | 0.11455 (11) | 0.0325 (6) | |
H37 | 0.5394 | 0.2830 | 0.1533 | 0.039* | |
C38 | 0.2818 (3) | 0.3860 (4) | 0.19759 (14) | 0.0409 (7) | |
H38A | 0.2021 | 0.3730 | 0.1668 | 0.061* | |
H38C | 0.2655 | 0.4320 | 0.2360 | 0.061* | |
H38B | 0.3227 | 0.2778 | 0.2063 | 0.061* | |
C41 | 0.8471 (3) | 1.2483 (5) | 0.13378 (18) | 0.0555 (9) | |
H41C | 0.8456 | 1.3240 | 0.1682 | 0.083* | |
H41A | 0.7880 | 1.2872 | 0.0962 | 0.083* | |
H41B | 0.9320 | 1.2449 | 0.1264 | 0.083* | |
C51 | 0.7326 (3) | 0.6892 (4) | 0.14846 (12) | 0.0356 (6) | |
H51C | 0.7800 | 0.7845 | 0.1386 | 0.053* | |
H51A | 0.7091 | 0.6174 | 0.1119 | 0.053* | |
H51B | 0.7847 | 0.6269 | 0.1830 | 0.053* | |
H21B | 0.461 (3) | 0.009 (2) | 0.4576 (14) | 0.036 (8)* | |
H61B | 0.434 (4) | 0.4279 (14) | 0.3695 (19) | 0.067 (12)* | |
H31B | 0.541 (2) | 0.601 (3) | 0.2058 (13) | 0.039 (8)* | |
H21A | 0.454 (3) | 0.179 (4) | 0.4372 (13) | 0.051 (10)* | |
H41 | 0.756 (3) | 1.107 (7) | 0.1776 (16) | 0.085 (15)* | |
H21C | 0.454 (2) | 0.141 (4) | 0.5107 (6) | 0.029 (7)* | |
H31A | 0.524 (3) | 0.427 (2) | 0.2353 (14) | 0.041 (8)* | |
H51 | 0.650 (3) | 0.843 (3) | 0.1925 (15) | 0.063 (11)* | |
H31C | 0.464 (3) | 0.582 (4) | 0.2564 (10) | 0.037 (8)* | |
H61A | 0.489 (3) | 0.277 (6) | 0.3425 (15) | 0.072 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0381 (9) | 0.0137 (8) | 0.0272 (8) | 0.0002 (7) | 0.0150 (7) | 0.0000 (6) |
O2 | 0.0302 (8) | 0.0195 (8) | 0.0219 (7) | 0.0014 (7) | 0.0100 (6) | 0.0027 (7) |
O3 | 0.0298 (8) | 0.0141 (8) | 0.0274 (8) | 0.0030 (7) | 0.0105 (6) | 0.0026 (6) |
O4 | 0.0258 (7) | 0.0197 (8) | 0.0236 (7) | 0.0015 (7) | 0.0111 (6) | 0.0019 (7) |
O5 | 0.0185 (7) | 0.0174 (8) | 0.0215 (7) | 0.0028 (6) | 0.0064 (6) | 0.0018 (6) |
O6 | 0.0214 (7) | 0.0265 (9) | 0.0319 (8) | −0.0005 (7) | 0.0109 (6) | −0.0011 (7) |
O7 | 0.0179 (7) | 0.0139 (7) | 0.0236 (7) | 0.0030 (6) | 0.0063 (6) | 0.0011 (6) |
O8 | 0.0212 (7) | 0.0183 (8) | 0.0317 (8) | −0.0004 (6) | 0.0052 (6) | −0.0029 (7) |
O41 | 0.0675 (15) | 0.0475 (14) | 0.0702 (16) | −0.0074 (12) | 0.0432 (13) | −0.0048 (12) |
O61 | 0.0466 (10) | 0.0172 (9) | 0.0405 (10) | 0.0039 (8) | 0.0262 (8) | 0.0051 (8) |
N21 | 0.0318 (10) | 0.0188 (9) | 0.0214 (9) | 0.0010 (9) | 0.0088 (8) | −0.0004 (8) |
N31 | 0.0310 (10) | 0.0155 (9) | 0.0228 (9) | 0.0020 (8) | 0.0095 (7) | −0.0001 (8) |
C1 | 0.0206 (10) | 0.0131 (10) | 0.0260 (11) | 0.0035 (8) | 0.0125 (8) | 0.0024 (8) |
C2 | 0.0200 (10) | 0.0146 (10) | 0.0196 (9) | 0.0019 (8) | 0.0068 (8) | 0.0001 (8) |
C3 | 0.0198 (9) | 0.0121 (10) | 0.0215 (10) | 0.0022 (8) | 0.0068 (8) | 0.0003 (8) |
C4 | 0.0154 (9) | 0.0164 (10) | 0.0222 (10) | −0.0006 (8) | 0.0040 (8) | 0.0017 (8) |
C5 | 0.0192 (9) | 0.0116 (10) | 0.0303 (11) | −0.0006 (8) | 0.0083 (8) | −0.0004 (9) |
C6 | 0.0223 (10) | 0.0158 (11) | 0.0289 (11) | 0.0020 (9) | 0.0040 (8) | −0.0004 (9) |
C7 | 0.0245 (10) | 0.0242 (12) | 0.0309 (11) | 0.0004 (10) | 0.0053 (9) | 0.0012 (10) |
C8 | 0.0326 (12) | 0.0379 (15) | 0.0308 (12) | 0.0009 (11) | 0.0069 (10) | 0.0058 (11) |
C9 | 0.0372 (13) | 0.0422 (16) | 0.0313 (13) | 0.0065 (12) | −0.0001 (11) | 0.0010 (12) |
C10 | 0.0238 (11) | 0.0530 (19) | 0.0410 (14) | 0.0045 (13) | −0.0002 (10) | −0.0049 (14) |
C11 | 0.0228 (11) | 0.0379 (15) | 0.0362 (13) | 0.0011 (11) | 0.0055 (9) | −0.0025 (12) |
C12 | 0.0496 (17) | 0.085 (3) | 0.0347 (15) | 0.0104 (19) | −0.0046 (13) | 0.0061 (18) |
C13 | 0.0185 (9) | 0.0180 (11) | 0.0185 (9) | 0.0019 (9) | 0.0044 (8) | 0.0021 (8) |
C14 | 0.0192 (10) | 0.0179 (11) | 0.0178 (9) | 0.0027 (9) | 0.0041 (8) | 0.0011 (8) |
C15 | 0.0222 (10) | 0.0204 (11) | 0.0273 (11) | −0.0019 (9) | 0.0072 (9) | −0.0019 (9) |
C16 | 0.0192 (10) | 0.0269 (13) | 0.0371 (12) | 0.0003 (10) | 0.0126 (9) | −0.0031 (10) |
C17 | 0.0259 (11) | 0.0218 (12) | 0.0313 (12) | 0.0041 (10) | 0.0112 (9) | 0.0015 (10) |
C18 | 0.0288 (12) | 0.0152 (11) | 0.0402 (13) | 0.0007 (9) | 0.0138 (10) | 0.0027 (10) |
C19 | 0.0186 (10) | 0.0198 (11) | 0.0303 (11) | 0.0000 (9) | 0.0084 (8) | 0.0023 (10) |
C20 | 0.0319 (13) | 0.0253 (13) | 0.0494 (16) | 0.0066 (11) | 0.0162 (11) | 0.0008 (12) |
C21 | 0.0281 (11) | 0.0268 (12) | 0.0243 (11) | −0.0001 (10) | 0.0042 (9) | 0.0036 (10) |
C22 | 0.0297 (11) | 0.0272 (13) | 0.0245 (11) | 0.0014 (10) | 0.0060 (9) | 0.0044 (10) |
C23 | 0.104 (3) | 0.079 (3) | 0.0295 (15) | −0.058 (3) | −0.0200 (17) | 0.0237 (17) |
C24 | 0.098 (3) | 0.087 (3) | 0.050 (2) | −0.065 (3) | −0.027 (2) | 0.030 (2) |
C25 | 0.0457 (15) | 0.0374 (16) | 0.0430 (15) | −0.0041 (13) | 0.0133 (12) | 0.0163 (13) |
C26 | 0.0597 (17) | 0.0288 (14) | 0.0255 (12) | 0.0056 (13) | 0.0153 (11) | 0.0050 (11) |
C27 | 0.0525 (15) | 0.0274 (13) | 0.0217 (11) | −0.0005 (12) | 0.0060 (10) | −0.0007 (10) |
C28 | 0.0367 (14) | 0.0302 (15) | 0.0467 (15) | 0.0085 (12) | 0.0122 (12) | 0.0071 (12) |
C31 | 0.0277 (11) | 0.0192 (12) | 0.0322 (12) | 0.0047 (10) | 0.0061 (9) | −0.0010 (10) |
C32 | 0.0259 (11) | 0.0204 (12) | 0.0253 (10) | −0.0034 (9) | 0.0054 (8) | 0.0011 (9) |
C33 | 0.0342 (12) | 0.0300 (14) | 0.0344 (13) | −0.0034 (11) | −0.0029 (10) | 0.0058 (11) |
C34 | 0.0489 (16) | 0.0490 (18) | 0.0238 (12) | −0.0172 (15) | −0.0038 (11) | 0.0078 (13) |
C35 | 0.0481 (16) | 0.063 (2) | 0.0244 (12) | −0.0205 (16) | 0.0121 (11) | −0.0118 (14) |
C36 | 0.0384 (14) | 0.057 (2) | 0.0367 (14) | 0.0056 (14) | 0.0096 (11) | −0.0159 (14) |
C37 | 0.0356 (12) | 0.0362 (15) | 0.0236 (11) | 0.0081 (12) | 0.0027 (9) | −0.0032 (11) |
C38 | 0.0367 (14) | 0.0472 (17) | 0.0448 (15) | −0.0086 (13) | 0.0218 (12) | −0.0116 (14) |
C41 | 0.0544 (19) | 0.049 (2) | 0.066 (2) | −0.0035 (17) | 0.0207 (16) | 0.0036 (18) |
C51 | 0.0417 (14) | 0.0385 (15) | 0.0286 (12) | 0.0071 (13) | 0.0121 (11) | 0.0028 (12) |
Geometric parameters (Å, º) top
O1—C1 | 1.251 (3) | C16—H16 | 0.9500 |
O2—C1 | 1.251 (3) | C17—C18 | 1.398 (3) |
O3—C4 | 1.257 (3) | C17—C20 | 1.506 (3) |
O4—C4 | 1.240 (3) | C18—C19 | 1.381 (3) |
O5—C2 | 1.445 (2) | C18—H18 | 0.9500 |
O7—C3 | 1.437 (2) | C19—H19 | 0.9500 |
C1—C2 | 1.537 (3) | C20—H20C | 0.9800 |
C2—C3 | 1.520 (3) | C20—H20A | 0.9800 |
C3—C4 | 1.547 (3) | C20—H20B | 0.9800 |
O7—C13 | 1.366 (2) | C21—C22 | 1.507 (4) |
O6—C5 | 1.207 (3) | C21—C28 | 1.519 (4) |
O5—C5 | 1.355 (2) | C21—H21 | 1.0000 |
O8—C13 | 1.204 (3) | C22—C23 | 1.375 (4) |
O41—C41 | 1.387 (5) | C22—C27 | 1.383 (3) |
O41—H41 | 1.00 (4) | C23—C24 | 1.387 (5) |
O51—C51 | 1.425 (3) | C23—H23 | 0.9500 |
O51—H51 | 0.99 (3) | C24—C25 | 1.375 (5) |
O61—H61B | 0.944 (12) | C24—H24 | 0.9500 |
O61—H61A | 0.94 (3) | C25—C26 | 1.379 (4) |
N21—C21 | 1.509 (3) | C25—H25 | 0.9500 |
N21—H21B | 0.95 (3) | C26—C27 | 1.379 (4) |
N21—H21A | 0.96 (3) | C26—H26 | 0.9500 |
N21—H21C | 0.959 (10) | C27—H27 | 0.9500 |
N31—C31 | 1.495 (3) | C28—H28A | 0.9800 |
N31—H31B | 0.958 (10) | C28—H28C | 0.9800 |
N31—H31A | 0.953 (10) | C28—H28B | 0.9800 |
N31—H31C | 0.95 (3) | C31—C32 | 1.509 (3) |
C2—H2 | 1.0000 | C31—C38 | 1.522 (4) |
C3—H3 | 1.0000 | C31—H31 | 1.0000 |
C5—C6 | 1.483 (3) | C32—C37 | 1.383 (3) |
C6—C7 | 1.386 (3) | C32—C33 | 1.393 (3) |
C6—C11 | 1.399 (3) | C33—C34 | 1.385 (4) |
C7—C8 | 1.384 (3) | C33—H33 | 0.9500 |
C7—H7 | 0.9500 | C34—C35 | 1.372 (5) |
C8—C9 | 1.393 (4) | C34—H34 | 0.9500 |
C8—H8 | 0.9500 | C35—C36 | 1.382 (4) |
C9—C10 | 1.387 (4) | C35—H35 | 0.9500 |
C9—C12 | 1.509 (4) | C36—C37 | 1.386 (4) |
C10—C11 | 1.376 (4) | C36—H36 | 0.9500 |
C10—H10 | 0.9500 | C37—H37 | 0.9500 |
C11—H11 | 0.9500 | C38—H38A | 0.9800 |
C12—H12C | 0.9800 | C38—H38C | 0.9800 |
C12—H12B | 0.9800 | C38—H38B | 0.9800 |
C12—H12A | 0.9800 | C41—H41C | 0.9800 |
C13—C14 | 1.478 (3) | C41—H41A | 0.9800 |
C14—C15 | 1.388 (3) | C41—H41B | 0.9800 |
C14—C19 | 1.395 (3) | C51—H51C | 0.9800 |
C15—C16 | 1.383 (3) | C51—H51A | 0.9800 |
C15—H15 | 0.9500 | C51—H51B | 0.9800 |
C16—C17 | 1.389 (4) | | |
| | | |
C5—O5—C2 | 114.60 (15) | C18—C19—H19 | 120.0 |
C13—O7—C3 | 113.48 (16) | C14—C19—H19 | 120.0 |
C41—O41—H41 | 106 (3) | C17—C20—H20C | 109.5 |
C51—O51—H51 | 105 (2) | C17—C20—H20A | 109.5 |
H61B—O61—H61A | 109 (4) | H20C—C20—H20A | 109.5 |
C21—N21—H21B | 109.9 (19) | C17—C20—H20B | 109.5 |
C21—N21—H21A | 107 (2) | H20C—C20—H20B | 109.5 |
H21B—N21—H21A | 97 (3) | H20A—C20—H20B | 109.5 |
C21—N21—H21C | 108.9 (16) | C22—C21—N21 | 111.0 (2) |
H21B—N21—H21C | 114 (3) | C22—C21—C28 | 113.8 (2) |
H21A—N21—H21C | 119 (3) | N21—C21—C28 | 108.8 (2) |
C31—N31—H31B | 109.9 (18) | C22—C21—H21 | 107.7 |
C31—N31—H31A | 110 (2) | N21—C21—H21 | 107.7 |
H31B—N31—H31A | 111 (3) | C28—C21—H21 | 107.7 |
C31—N31—H31C | 109.7 (18) | C23—C22—C27 | 118.2 (3) |
H31B—N31—H31C | 109 (3) | C23—C22—C21 | 119.5 (2) |
H31A—N31—H31C | 107 (3) | C27—C22—C21 | 122.4 (2) |
O2—C1—O1 | 127.5 (2) | C22—C23—C24 | 121.3 (3) |
O2—C1—C2 | 115.11 (19) | C22—C23—H23 | 119.3 |
O1—C1—C2 | 117.36 (18) | C24—C23—H23 | 119.3 |
O5—C2—C3 | 106.40 (16) | C25—C24—C23 | 120.2 (3) |
O5—C2—C1 | 113.17 (18) | C25—C24—H24 | 119.9 |
C3—C2—C1 | 111.48 (17) | C23—C24—H24 | 119.9 |
O5—C2—H2 | 108.6 | C24—C25—C26 | 118.6 (3) |
C3—C2—H2 | 108.6 | C24—C25—H25 | 120.7 |
C1—C2—H2 | 108.6 | C26—C25—H25 | 120.7 |
O7—C3—C2 | 107.91 (17) | C27—C26—C25 | 121.0 (2) |
O7—C3—C4 | 111.45 (16) | C27—C26—H26 | 119.5 |
C2—C3—C4 | 110.22 (16) | C25—C26—H26 | 119.5 |
O7—C3—H3 | 109.1 | C26—C27—C22 | 120.6 (3) |
C2—C3—H3 | 109.1 | C26—C27—H27 | 119.7 |
C4—C3—H3 | 109.1 | C22—C27—H27 | 119.7 |
O4—C4—O3 | 126.6 (2) | C21—C28—H28A | 109.5 |
O4—C4—C3 | 119.19 (19) | C21—C28—H28C | 109.5 |
O3—C4—C3 | 114.16 (18) | H28A—C28—H28C | 109.5 |
O6—C5—O5 | 122.56 (19) | C21—C28—H28B | 109.5 |
O6—C5—C6 | 125.49 (19) | H28A—C28—H28B | 109.5 |
O5—C5—C6 | 111.91 (17) | H28C—C28—H28B | 109.5 |
C7—C6—C11 | 119.3 (2) | N31—C31—C32 | 111.13 (18) |
C7—C6—C5 | 122.5 (2) | N31—C31—C38 | 108.8 (2) |
C11—C6—C5 | 118.0 (2) | C32—C31—C38 | 112.1 (2) |
C8—C7—C6 | 120.2 (2) | N31—C31—H31 | 108.3 |
C8—C7—H7 | 119.9 | C32—C31—H31 | 108.3 |
C6—C7—H7 | 119.9 | C38—C31—H31 | 108.3 |
C7—C8—C9 | 120.7 (2) | C37—C32—C33 | 119.0 (2) |
C7—C8—H8 | 119.7 | C37—C32—C31 | 121.7 (2) |
C9—C8—H8 | 119.7 | C33—C32—C31 | 119.2 (2) |
C10—C9—C8 | 118.6 (2) | C34—C33—C32 | 120.3 (3) |
C10—C9—C12 | 120.8 (3) | C34—C33—H33 | 119.8 |
C8—C9—C12 | 120.6 (3) | C32—C33—H33 | 119.8 |
C11—C10—C9 | 121.3 (2) | C35—C34—C33 | 120.4 (2) |
C11—C10—H10 | 119.3 | C35—C34—H34 | 119.8 |
C9—C10—H10 | 119.3 | C33—C34—H34 | 119.8 |
C10—C11—C6 | 119.8 (2) | C34—C35—C36 | 119.7 (3) |
C10—C11—H11 | 120.1 | C34—C35—H35 | 120.2 |
C6—C11—H11 | 120.1 | C36—C35—H35 | 120.2 |
C9—C12—H12C | 109.5 | C35—C36—C37 | 120.4 (3) |
C9—C12—H12B | 109.5 | C35—C36—H36 | 119.8 |
H12C—C12—H12B | 109.5 | C37—C36—H36 | 119.8 |
C9—C12—H12A | 109.5 | C32—C37—C36 | 120.2 (2) |
H12C—C12—H12A | 109.5 | C32—C37—H37 | 119.9 |
H12B—C12—H12A | 109.5 | C36—C37—H37 | 119.9 |
O8—C13—O7 | 122.57 (19) | C31—C38—H38A | 109.5 |
O8—C13—C14 | 124.99 (19) | C31—C38—H38C | 109.5 |
O7—C13—C14 | 112.43 (18) | H38A—C38—H38C | 109.5 |
C15—C14—C19 | 119.3 (2) | C31—C38—H38B | 109.5 |
C15—C14—C13 | 117.9 (2) | H38A—C38—H38B | 109.5 |
C19—C14—C13 | 122.76 (18) | H38C—C38—H38B | 109.5 |
C16—C15—C14 | 120.1 (2) | O41—C41—H41C | 109.5 |
C16—C15—H15 | 119.9 | O41—C41—H41A | 109.5 |
C14—C15—H15 | 119.9 | H41C—C41—H41A | 109.5 |
C15—C16—C17 | 121.16 (19) | O41—C41—H41B | 109.5 |
C15—C16—H16 | 119.4 | H41C—C41—H41B | 109.5 |
C17—C16—H16 | 119.4 | H41A—C41—H41B | 109.5 |
C16—C17—C18 | 118.3 (2) | O51—C51—H51C | 109.5 |
C16—C17—C20 | 121.8 (2) | O51—C51—H51A | 109.5 |
C18—C17—C20 | 119.9 (2) | H51C—C51—H51A | 109.5 |
C19—C18—C17 | 120.9 (2) | O51—C51—H51B | 109.5 |
C19—C18—H18 | 119.6 | H51C—C51—H51B | 109.5 |
C17—C18—H18 | 119.6 | H51A—C51—H51B | 109.5 |
C18—C19—C14 | 120.10 (19) | | |
| | | |
C5—O5—C2—C3 | −156.8 (2) | O8—C13—C14—C19 | 162.0 (2) |
C5—O5—C2—C1 | 80.5 (2) | O7—C13—C14—C19 | −17.5 (3) |
O2—C1—C2—O5 | −167.05 (17) | C19—C14—C15—C16 | −2.7 (3) |
O1—C1—C2—O5 | 14.9 (3) | C13—C14—C15—C16 | 175.3 (2) |
O2—C1—C2—C3 | 73.1 (2) | C14—C15—C16—C17 | 1.2 (4) |
O1—C1—C2—C3 | −105.0 (2) | C15—C16—C17—C18 | 1.6 (4) |
C13—O7—C3—C2 | −171.0 (2) | C15—C16—C17—C20 | −178.7 (3) |
C13—O7—C3—C4 | 67.9 (2) | C16—C17—C18—C19 | −2.9 (4) |
O5—C2—C3—O7 | −76.3 (2) | C20—C17—C18—C19 | 177.4 (2) |
C1—C2—C3—O7 | 47.5 (2) | C17—C18—C19—C14 | 1.4 (4) |
O5—C2—C3—C4 | 45.6 (2) | C15—C14—C19—C18 | 1.5 (3) |
C1—C2—C3—C4 | 169.39 (17) | C13—C14—C19—C18 | −176.5 (2) |
O7—C3—C4—O4 | 12.6 (3) | N21—C21—C22—C23 | −127.8 (3) |
C2—C3—C4—O4 | −107.2 (2) | C28—C21—C22—C23 | 109.1 (4) |
O7—C3—C4—O3 | −168.47 (17) | N21—C21—C22—C27 | 53.2 (3) |
C2—C3—C4—O3 | 71.7 (2) | C28—C21—C22—C27 | −69.9 (3) |
C2—O5—C5—O6 | −12.1 (3) | C27—C22—C23—C24 | 0.7 (7) |
C2—O5—C5—C6 | 165.5 (2) | C21—C22—C23—C24 | −178.3 (4) |
O6—C5—C6—C7 | 164.0 (2) | C22—C23—C24—C25 | −0.1 (8) |
O5—C5—C6—C7 | −13.6 (3) | C23—C24—C25—C26 | −1.4 (7) |
O6—C5—C6—C11 | −11.4 (4) | C24—C25—C26—C27 | 2.3 (5) |
O5—C5—C6—C11 | 171.0 (2) | C25—C26—C27—C22 | −1.7 (4) |
C11—C6—C7—C8 | 0.6 (4) | C23—C22—C27—C26 | 0.2 (5) |
C5—C6—C7—C8 | −174.8 (2) | C21—C22—C27—C26 | 179.2 (2) |
C6—C7—C8—C9 | −0.1 (4) | N31—C31—C32—C37 | 40.2 (3) |
C7—C8—C9—C10 | −0.8 (5) | C38—C31—C32—C37 | −81.7 (3) |
C7—C8—C9—C12 | 177.5 (3) | N31—C31—C32—C33 | −143.7 (2) |
C8—C9—C10—C11 | 1.2 (5) | C38—C31—C32—C33 | 94.4 (3) |
C12—C9—C10—C11 | −177.1 (3) | C37—C32—C33—C34 | −0.3 (4) |
C9—C10—C11—C6 | −0.7 (5) | C31—C32—C33—C34 | −176.5 (2) |
C7—C6—C11—C10 | −0.2 (4) | C32—C33—C34—C35 | −1.5 (4) |
C5—C6—C11—C10 | 175.4 (3) | C33—C34—C35—C36 | 1.9 (5) |
C3—O7—C13—O8 | 2.5 (3) | C34—C35—C36—C37 | −0.5 (5) |
C3—O7—C13—C14 | −178.0 (2) | C33—C32—C37—C36 | 1.6 (4) |
O8—C13—C14—C15 | −16.0 (3) | C31—C32—C37—C36 | 177.8 (3) |
O7—C13—C14—C15 | 164.54 (19) | C35—C36—C37—C32 | −1.2 (5) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···O61 | 0.95 (3) | 1.80 (2) | 2.716 (3) | 158 (3) |
N21—H21B···O2i | 0.96 (1) | 1.99 (1) | 2.929 (3) | 166 (3) |
N21—H21C···O2ii | 0.95 (1) | 1.95 (2) | 2.846 (3) | 155 (3) |
N31—H31A···O3i | 0.95 (3) | 1.87 (1) | 2.795 (3) | 162 (3) |
N31—H31B···O51 | 0.96 (1) | 1.82 (1) | 2.768 (3) | 170 (3) |
N31—H31C···O1 | 0.95 (3) | 1.92 (1) | 2.843 (2) | 165 (3) |
O41—H41···O4 | 1.00 (4) | 1.82 (2) | 2.767 (3) | 158 (5) |
O51—H51···O4 | 0.99 (3) | 1.82 (2) | 2.757 (3) | 158 (3) |
O61—H61A···O3i | 0.94 (3) | 1.81 (3) | 2.750 (2) | 172 (4) |
O61—H61B···O1 | 0.94 (1) | 1.80 (2) | 2.687 (2) | 156 (4) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1. |
(II) Bis(benylammonium) (2
R,3
R)-(-)-2,3-di-
p-toluoyloxybutanedioate dihydrate
top
Crystal data top
2C7H10N+·C20H16O82−·2H2O | Dx = 1.249 Mg m−3 |
Mr = 636.68 | Melting point: not measured K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 28526 reflections |
a = 6.8805 (1) Å | θ = 4.3–27.2° |
b = 19.2606 (1) Å | µ = 0.09 mm−1 |
c = 25.5545 (2) Å | T = 113 K |
V = 3386.55 (6) Å3 | Prism, colourless |
Z = 4 | 0.35 × 0.25 × 0.25 mm |
F(000) = 1352 | |
Data collection top
Nonius Kappa CCD area-detector diffractometer | 3955 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 27.2°, θmin = 4.3° |
1.2° ϕ scans and ω scans | h = −8→8 |
28533 measured reflections | k = −24→24 |
4225 independent reflections | l = −32→32 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.084 | w = 1/[σ2(Fo2) + (0.048P)2 + 0.6428P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
4225 reflections | Δρmax = 0.28 e Å−3 |
458 parameters | Δρmin = −0.26 e Å−3 |
10 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.017 (2) |
Crystal data top
2C7H10N+·C20H16O82−·2H2O | V = 3386.55 (6) Å3 |
Mr = 636.68 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.8805 (1) Å | µ = 0.09 mm−1 |
b = 19.2606 (1) Å | T = 113 K |
c = 25.5545 (2) Å | 0.35 × 0.25 × 0.25 mm |
Data collection top
Nonius Kappa CCD area-detector diffractometer | 3955 reflections with I > 2σ(I) |
28533 measured reflections | Rint = 0.027 |
4225 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 10 restraints |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.28 e Å−3 |
4225 reflections | Δρmin = −0.26 e Å−3 |
458 parameters | |
Special details top
Experimental. Half sphere of data collected using COLLECT strategy (Nonius, 2000). Crystal to detector distance = 36 mm; combination of ϕ and ω scans of 1.2°, 60 s per °, 2 iterations. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.33566 (17) | 0.03978 (6) | 0.28175 (5) | 0.0244 (3) | |
O2 | 0.64601 (18) | 0.03542 (6) | 0.25560 (5) | 0.0253 (3) | |
O3 | 0.26410 (17) | 0.28670 (6) | 0.24921 (5) | 0.0230 (3) | |
O4 | 0.57696 (18) | 0.29712 (6) | 0.27143 (5) | 0.0251 (3) | |
O5 | 0.62623 (17) | 0.16345 (5) | 0.21189 (4) | 0.0205 (2) | |
O6 | 0.51992 (19) | 0.10642 (6) | 0.14061 (5) | 0.0295 (3) | |
O7 | 0.55520 (16) | 0.17262 (5) | 0.32548 (4) | 0.0195 (2) | |
O8 | 0.3413 (2) | 0.21682 (10) | 0.38221 (6) | 0.0542 (5) | |
O41 | 0.1472 (2) | 0.41262 (6) | 0.20589 (6) | 0.0307 (3) | |
O51 | 0.98173 (18) | 0.10972 (6) | 0.28272 (5) | 0.0290 (3) | |
N21 | 0.7301 (2) | 0.40433 (7) | 0.20404 (6) | 0.0266 (3) | |
N31 | 0.9297 (2) | 0.25097 (7) | 0.30575 (6) | 0.0247 (3) | |
C1 | 0.4861 (2) | 0.06404 (8) | 0.26049 (6) | 0.0196 (3) | |
C2 | 0.4579 (2) | 0.13857 (7) | 0.23949 (6) | 0.0187 (3) | |
H2 | 0.3443 | 0.1389 | 0.2151 | 0.022* | |
C3 | 0.4158 (2) | 0.18741 (7) | 0.28461 (6) | 0.0181 (3) | |
H3 | 0.2828 | 0.1769 | 0.2983 | 0.022* | |
C4 | 0.4212 (2) | 0.26425 (8) | 0.26732 (6) | 0.0185 (3) | |
C5 | 0.6402 (3) | 0.14244 (8) | 0.16165 (6) | 0.0215 (3) | |
C6 | 0.8176 (3) | 0.16925 (8) | 0.13568 (6) | 0.0221 (3) | |
C7 | 0.9560 (3) | 0.20864 (8) | 0.16180 (7) | 0.0256 (3) | |
H7 | 0.9379 | 0.2199 | 0.1977 | 0.031* | |
C8 | 1.1202 (3) | 0.23148 (10) | 0.13565 (7) | 0.0298 (4) | |
H8 | 1.2137 | 0.2587 | 0.1538 | 0.036* | |
C9 | 1.1503 (3) | 0.21518 (9) | 0.08327 (7) | 0.0294 (4) | |
C10 | 1.0125 (3) | 0.17495 (10) | 0.05773 (7) | 0.0301 (4) | |
H10 | 1.0321 | 0.1629 | 0.0221 | 0.036* | |
C11 | 0.8476 (3) | 0.15219 (9) | 0.08319 (7) | 0.0274 (4) | |
H11 | 0.7545 | 0.1249 | 0.0650 | 0.033* | |
C12 | 1.3301 (3) | 0.24014 (13) | 0.05544 (8) | 0.0447 (5) | |
H12A | 1.3175 | 0.2311 | 0.0179 | 0.067* | |
H12C | 1.4439 | 0.2155 | 0.0691 | 0.067* | |
H12B | 1.3459 | 0.2901 | 0.0613 | 0.067* | |
C13 | 0.4907 (3) | 0.18590 (9) | 0.37432 (7) | 0.0269 (4) | |
C14 | 0.6260 (3) | 0.16301 (9) | 0.41548 (7) | 0.0257 (4) | |
C15 | 0.7930 (3) | 0.12479 (9) | 0.40495 (7) | 0.0290 (4) | |
H15 | 0.8176 | 0.1086 | 0.3705 | 0.035* | |
C16 | 0.9229 (3) | 0.11047 (10) | 0.44471 (8) | 0.0388 (5) | |
H16 | 1.0377 | 0.0849 | 0.4372 | 0.047* | |
C17 | 0.8877 (4) | 0.13302 (11) | 0.49569 (8) | 0.0430 (5) | |
C18 | 0.7170 (4) | 0.16865 (12) | 0.50588 (8) | 0.0443 (5) | |
H18 | 0.6886 | 0.1826 | 0.5407 | 0.053* | |
C19 | 0.5884 (3) | 0.18407 (11) | 0.46668 (7) | 0.0363 (4) | |
H19 | 0.4732 | 0.2092 | 0.4744 | 0.044* | |
C20 | 1.0316 (5) | 0.11925 (15) | 0.53895 (10) | 0.0644 (8) | |
H20C | 1.0048 | 0.0738 | 0.5546 | 0.097* | |
H20B | 1.0199 | 0.1554 | 0.5657 | 0.097* | |
H20A | 1.1637 | 0.1196 | 0.5246 | 0.097* | |
C21 | 0.6365 (3) | 0.36911 (9) | 0.15866 (8) | 0.0343 (4) | |
H21D | 0.4957 | 0.3644 | 0.1658 | 0.041* | |
H21E | 0.6913 | 0.3218 | 0.1553 | 0.041* | |
C22 | 0.6627 (4) | 0.40659 (9) | 0.10768 (8) | 0.0358 (5) | |
C23 | 0.5155 (5) | 0.44949 (11) | 0.08932 (10) | 0.0578 (7) | |
H23 | 0.4028 | 0.4565 | 0.1101 | 0.069* | |
C24 | 0.5300 (8) | 0.48183 (14) | 0.04171 (12) | 0.0810 (12) | |
H24 | 0.4287 | 0.5114 | 0.0299 | 0.097* | |
C25 | 0.6880 (8) | 0.47153 (16) | 0.01180 (12) | 0.0855 (13) | |
H25 | 0.6954 | 0.4929 | −0.0216 | 0.103* | |
C26 | 0.8398 (6) | 0.4304 (2) | 0.02885 (12) | 0.0846 (12) | |
H26 | 0.9522 | 0.4246 | 0.0077 | 0.102* | |
C27 | 0.8269 (5) | 0.39682 (15) | 0.07807 (10) | 0.0578 (7) | |
H27 | 0.9296 | 0.3682 | 0.0903 | 0.069* | |
C31 | 0.9356 (3) | 0.28543 (8) | 0.35819 (7) | 0.0275 (4) | |
H31E | 1.0503 | 0.2687 | 0.3779 | 0.033* | |
H31D | 0.8177 | 0.2728 | 0.3783 | 0.033* | |
C32 | 0.9460 (3) | 0.36328 (8) | 0.35255 (6) | 0.0244 (3) | |
C33 | 1.1244 (3) | 0.39668 (11) | 0.35171 (9) | 0.0385 (5) | |
H33 | 1.2412 | 0.3707 | 0.3546 | 0.046* | |
C34 | 1.1310 (4) | 0.46842 (13) | 0.34660 (10) | 0.0531 (7) | |
H34 | 1.2529 | 0.4916 | 0.3462 | 0.064* | |
C35 | 0.9626 (5) | 0.50598 (10) | 0.34212 (9) | 0.0534 (7) | |
H35 | 0.9687 | 0.5550 | 0.3384 | 0.064* | |
C36 | 0.7850 (4) | 0.47338 (10) | 0.34293 (8) | 0.0408 (5) | |
H36 | 0.6687 | 0.4997 | 0.3401 | 0.049* | |
C37 | 0.7766 (3) | 0.40159 (9) | 0.34785 (7) | 0.0278 (4) | |
H37 | 0.6542 | 0.3787 | 0.3480 | 0.033* | |
H21A | 0.8687 (15) | 0.4048 (13) | 0.2000 (9) | 0.041 (6)* | |
H31A | 1.031 (3) | 0.2643 (12) | 0.2826 (7) | 0.039 (6)* | |
H41A | 0.201 (4) | 0.3767 (10) | 0.2261 (9) | 0.054 (7)* | |
H21B | 0.691 (3) | 0.3812 (10) | 0.2352 (6) | 0.030 (5)* | |
H31B | 0.942 (4) | 0.2020 (5) | 0.3098 (9) | 0.043 (6)* | |
H41B | 0.211 (5) | 0.4508 (12) | 0.2210 (12) | 0.079 (10)* | |
H51B | 0.877 (3) | 0.0874 (12) | 0.2666 (9) | 0.049 (7)* | |
H21C | 0.695 (4) | 0.4519 (6) | 0.2091 (9) | 0.043 (6)* | |
H31C | 0.809 (2) | 0.2630 (11) | 0.2897 (8) | 0.030 (5)* | |
H51A | 1.091 (3) | 0.0805 (11) | 0.2825 (10) | 0.052 (7)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0205 (6) | 0.0160 (5) | 0.0368 (6) | −0.0019 (5) | 0.0028 (5) | 0.0024 (5) |
O2 | 0.0200 (6) | 0.0175 (5) | 0.0384 (7) | 0.0032 (5) | 0.0007 (5) | −0.0010 (5) |
O3 | 0.0188 (6) | 0.0181 (5) | 0.0320 (6) | 0.0009 (5) | −0.0034 (5) | 0.0019 (5) |
O4 | 0.0206 (6) | 0.0163 (5) | 0.0385 (6) | −0.0018 (5) | −0.0011 (5) | 0.0020 (5) |
O5 | 0.0190 (6) | 0.0191 (5) | 0.0234 (5) | −0.0023 (4) | 0.0028 (5) | −0.0013 (4) |
O6 | 0.0287 (7) | 0.0297 (6) | 0.0300 (6) | −0.0062 (6) | 0.0001 (5) | −0.0045 (5) |
O7 | 0.0172 (5) | 0.0189 (5) | 0.0223 (5) | 0.0007 (5) | −0.0002 (5) | 0.0004 (4) |
O8 | 0.0374 (9) | 0.0924 (13) | 0.0326 (7) | 0.0332 (10) | −0.0003 (7) | −0.0118 (8) |
O41 | 0.0301 (7) | 0.0214 (6) | 0.0406 (7) | 0.0019 (5) | −0.0048 (6) | 0.0022 (5) |
O51 | 0.0186 (6) | 0.0218 (6) | 0.0465 (7) | 0.0011 (5) | −0.0016 (6) | −0.0076 (5) |
N21 | 0.0298 (8) | 0.0163 (6) | 0.0338 (8) | 0.0031 (6) | 0.0044 (7) | 0.0007 (6) |
N31 | 0.0167 (6) | 0.0184 (6) | 0.0388 (8) | 0.0001 (6) | 0.0006 (6) | −0.0014 (6) |
C1 | 0.0201 (8) | 0.0151 (6) | 0.0237 (7) | −0.0007 (6) | −0.0024 (6) | −0.0025 (6) |
C2 | 0.0158 (7) | 0.0164 (6) | 0.0240 (7) | −0.0011 (6) | −0.0001 (6) | −0.0004 (6) |
C3 | 0.0148 (7) | 0.0163 (7) | 0.0233 (7) | 0.0001 (6) | −0.0013 (6) | 0.0006 (6) |
C4 | 0.0175 (7) | 0.0155 (7) | 0.0224 (7) | 0.0007 (6) | 0.0018 (6) | −0.0020 (6) |
C5 | 0.0237 (8) | 0.0159 (6) | 0.0248 (7) | 0.0024 (7) | 0.0000 (7) | −0.0005 (6) |
C6 | 0.0233 (8) | 0.0182 (7) | 0.0247 (8) | 0.0042 (7) | 0.0023 (7) | 0.0011 (6) |
C7 | 0.0277 (9) | 0.0247 (8) | 0.0245 (8) | −0.0011 (7) | 0.0032 (7) | 0.0005 (6) |
C8 | 0.0278 (9) | 0.0306 (8) | 0.0311 (9) | −0.0050 (8) | 0.0020 (7) | 0.0009 (7) |
C9 | 0.0267 (9) | 0.0316 (9) | 0.0300 (9) | 0.0038 (8) | 0.0050 (8) | 0.0096 (7) |
C10 | 0.0324 (10) | 0.0363 (9) | 0.0216 (8) | 0.0074 (8) | 0.0031 (7) | 0.0037 (7) |
C11 | 0.0281 (9) | 0.0301 (8) | 0.0241 (8) | 0.0019 (8) | −0.0009 (7) | −0.0014 (7) |
C12 | 0.0374 (11) | 0.0604 (13) | 0.0362 (10) | −0.0079 (11) | 0.0107 (10) | 0.0103 (10) |
C13 | 0.0263 (9) | 0.0292 (8) | 0.0253 (8) | 0.0026 (7) | 0.0025 (7) | −0.0019 (7) |
C14 | 0.0272 (9) | 0.0249 (8) | 0.0250 (8) | −0.0006 (7) | 0.0000 (7) | 0.0027 (6) |
C15 | 0.0347 (10) | 0.0267 (8) | 0.0256 (8) | 0.0047 (8) | −0.0014 (8) | 0.0021 (7) |
C16 | 0.0429 (11) | 0.0368 (10) | 0.0366 (10) | 0.0117 (10) | −0.0065 (10) | 0.0013 (8) |
C17 | 0.0553 (14) | 0.0408 (10) | 0.0329 (10) | 0.0075 (11) | −0.0150 (10) | −0.0003 (8) |
C18 | 0.0579 (14) | 0.0494 (12) | 0.0256 (9) | 0.0107 (12) | −0.0035 (10) | −0.0036 (9) |
C19 | 0.0400 (11) | 0.0410 (10) | 0.0278 (9) | 0.0056 (9) | 0.0022 (8) | −0.0006 (8) |
C20 | 0.078 (2) | 0.0713 (17) | 0.0435 (12) | 0.0238 (17) | −0.0290 (14) | −0.0080 (12) |
C21 | 0.0395 (11) | 0.0227 (8) | 0.0408 (10) | −0.0046 (8) | 0.0030 (9) | −0.0025 (7) |
C22 | 0.0484 (12) | 0.0221 (8) | 0.0367 (10) | −0.0063 (9) | 0.0015 (9) | −0.0061 (7) |
C23 | 0.086 (2) | 0.0360 (11) | 0.0519 (13) | 0.0122 (13) | −0.0125 (14) | −0.0040 (10) |
C24 | 0.147 (4) | 0.0446 (13) | 0.0520 (15) | 0.005 (2) | −0.024 (2) | 0.0001 (12) |
C25 | 0.162 (4) | 0.0501 (15) | 0.0443 (15) | −0.038 (2) | −0.018 (2) | 0.0026 (12) |
C26 | 0.104 (3) | 0.094 (2) | 0.0558 (16) | −0.048 (2) | 0.0332 (19) | −0.0228 (17) |
C27 | 0.0596 (16) | 0.0585 (14) | 0.0551 (14) | −0.0141 (14) | 0.0160 (13) | −0.0103 (12) |
C31 | 0.0266 (8) | 0.0223 (7) | 0.0336 (9) | 0.0012 (7) | 0.0004 (8) | 0.0015 (7) |
C32 | 0.0258 (9) | 0.0212 (7) | 0.0262 (8) | −0.0020 (7) | 0.0029 (7) | −0.0014 (6) |
C33 | 0.0331 (10) | 0.0378 (10) | 0.0444 (11) | −0.0105 (9) | 0.0048 (9) | −0.0035 (9) |
C34 | 0.0651 (17) | 0.0436 (12) | 0.0506 (13) | −0.0343 (13) | 0.0000 (12) | 0.0039 (11) |
C35 | 0.094 (2) | 0.0211 (9) | 0.0453 (11) | −0.0136 (12) | −0.0155 (14) | 0.0052 (8) |
C36 | 0.0649 (15) | 0.0232 (9) | 0.0344 (10) | 0.0109 (10) | −0.0106 (10) | −0.0038 (8) |
C37 | 0.0311 (9) | 0.0240 (8) | 0.0283 (9) | 0.0022 (7) | 0.0020 (8) | −0.0030 (7) |
Geometric parameters (Å, º) top
O1—C1 | 1.259 (2) | C14—C15 | 1.391 (3) |
O2—C1 | 1.237 (2) | C14—C19 | 1.394 (2) |
O3—C4 | 1.253 (2) | C15—C16 | 1.381 (3) |
O4—C4 | 1.249 (2) | C15—H15 | 0.9500 |
O5—C2 | 1.438 (2) | C16—C17 | 1.394 (3) |
O7—C3 | 1.446 (2) | C16—H16 | 0.9500 |
C1—C2 | 1.545 (2) | C17—C18 | 1.385 (3) |
C2—C3 | 1.516 (2) | C17—C20 | 1.508 (3) |
C3—C4 | 1.545 (2) | C18—C19 | 1.369 (3) |
O5—C5 | 1.350 (2) | C18—H18 | 0.9500 |
O6—C5 | 1.206 (2) | C19—H19 | 0.9500 |
O7—C13 | 1.349 (2) | C20—H20C | 0.9800 |
O8—C13 | 1.205 (2) | C20—H20B | 0.9800 |
O41—H41A | 0.939 (10) | C20—H20A | 0.9800 |
O41—H41B | 0.94 (3) | C21—C22 | 1.500 (3) |
O51—H51B | 0.937 (10) | C21—H21D | 0.9900 |
O51—H51A | 0.937 (10) | C21—H21E | 0.9900 |
N21—C21 | 1.490 (2) | C22—C27 | 1.373 (4) |
N21—H21A | 0.959 (10) | C22—C23 | 1.389 (4) |
N21—H21B | 0.951 (10) | C23—C24 | 1.371 (4) |
N21—H21C | 0.956 (10) | C23—H23 | 0.9500 |
N31—C31 | 1.496 (2) | C24—C25 | 1.343 (6) |
N31—H31A | 0.949 (10) | C24—H24 | 0.9500 |
N31—H31B | 0.952 (10) | C25—C26 | 1.382 (6) |
N31—H31C | 0.955 (10) | C25—H25 | 0.9500 |
C2—H2 | 1.0000 | C26—C27 | 1.417 (4) |
C3—H3 | 1.0000 | C26—H26 | 0.9500 |
C5—C6 | 1.482 (2) | C27—H27 | 0.9500 |
C6—C7 | 1.388 (2) | C31—C32 | 1.508 (2) |
C6—C11 | 1.397 (2) | C31—H31E | 0.9900 |
C7—C8 | 1.385 (3) | C31—H31D | 0.9900 |
C7—H7 | 0.9500 | C32—C37 | 1.385 (3) |
C8—C9 | 1.391 (3) | C32—C33 | 1.385 (3) |
C8—H8 | 0.9500 | C33—C34 | 1.389 (3) |
C9—C10 | 1.388 (3) | C33—H33 | 0.9500 |
C9—C12 | 1.505 (3) | C34—C35 | 1.371 (4) |
C10—C11 | 1.379 (3) | C34—H34 | 0.9500 |
C10—H10 | 0.9500 | C35—C36 | 1.374 (4) |
C11—H11 | 0.9500 | C35—H35 | 0.9500 |
C12—H12A | 0.9800 | C36—C37 | 1.390 (3) |
C12—H12C | 0.9800 | C36—H36 | 0.9500 |
C12—H12B | 0.9800 | C37—H37 | 0.9500 |
C13—C14 | 1.472 (3) | | |
| | | |
C5—O5—C2 | 115.08 (12) | C16—C15—H15 | 120.1 |
C13—O7—C3 | 114.37 (13) | C14—C15—H15 | 120.1 |
H41A—O41—H41B | 100 (2) | C15—C16—C17 | 120.8 (2) |
H51B—O51—H51A | 110 (2) | C15—C16—H16 | 119.6 |
C21—N21—H21A | 110.4 (15) | C17—C16—H16 | 119.6 |
C21—N21—H21B | 108.4 (13) | C18—C17—C16 | 118.51 (19) |
H21A—N21—H21B | 112 (2) | C18—C17—C20 | 120.4 (2) |
C21—N21—H21C | 115.6 (15) | C16—C17—C20 | 121.1 (2) |
H21A—N21—H21C | 105 (2) | C19—C18—C17 | 121.18 (19) |
H21B—N21—H21C | 105 (2) | C19—C18—H18 | 119.4 |
C31—N31—H31A | 114.7 (14) | C17—C18—H18 | 119.4 |
C31—N31—H31B | 109.9 (14) | C18—C19—C14 | 120.2 (2) |
H31A—N31—H31B | 106 (2) | C18—C19—H19 | 119.9 |
C31—N31—H31C | 107.5 (13) | C14—C19—H19 | 119.9 |
H31A—N31—H31C | 107.7 (17) | C17—C20—H20C | 109.5 |
H31B—N31—H31C | 111 (2) | C17—C20—H20B | 109.5 |
O2—C1—O1 | 127.56 (14) | H20C—C20—H20B | 109.5 |
O2—C1—C2 | 119.40 (14) | C17—C20—H20A | 109.5 |
O1—C1—C2 | 113.04 (14) | H20C—C20—H20A | 109.5 |
O5—C2—C3 | 108.66 (12) | H20B—C20—H20A | 109.5 |
O5—C2—C1 | 112.25 (13) | N21—C21—C22 | 113.89 (15) |
C3—C2—C1 | 109.66 (12) | N21—C21—H21D | 108.8 |
O5—C2—H2 | 108.7 | C22—C21—H21D | 108.8 |
C3—C2—H2 | 108.7 | N21—C21—H21E | 108.8 |
C1—C2—H2 | 108.7 | C22—C21—H21E | 108.8 |
O7—C3—C2 | 107.49 (12) | H21D—C21—H21E | 107.7 |
O7—C3—C4 | 112.29 (12) | C27—C22—C23 | 119.7 (2) |
C2—C3—C4 | 111.86 (12) | C27—C22—C21 | 120.8 (2) |
O7—C3—H3 | 108.4 | C23—C22—C21 | 119.5 (2) |
C2—C3—H3 | 108.4 | C24—C23—C22 | 121.1 (3) |
C4—C3—H3 | 108.4 | C24—C23—H23 | 119.4 |
O4—C4—O3 | 126.61 (13) | C22—C23—H23 | 119.4 |
O4—C4—C3 | 118.82 (14) | C25—C24—C23 | 119.8 (4) |
O3—C4—C3 | 114.56 (13) | C25—C24—H24 | 120.1 |
O6—C5—O5 | 123.22 (16) | C23—C24—H24 | 120.1 |
O6—C5—C6 | 124.45 (15) | C24—C25—C26 | 121.1 (3) |
O5—C5—C6 | 112.33 (14) | C24—C25—H25 | 119.4 |
C7—C6—C11 | 119.25 (16) | C26—C25—H25 | 119.4 |
C7—C6—C5 | 122.69 (15) | C25—C26—C27 | 119.6 (3) |
C11—C6—C5 | 118.04 (16) | C25—C26—H26 | 120.2 |
C8—C7—C6 | 120.10 (16) | C27—C26—H26 | 120.2 |
C8—C7—H7 | 119.9 | C22—C27—C26 | 118.6 (3) |
C6—C7—H7 | 119.9 | C22—C27—H27 | 120.7 |
C7—C8—C9 | 120.96 (18) | C26—C27—H27 | 120.7 |
C7—C8—H8 | 119.5 | N31—C31—C32 | 110.89 (14) |
C9—C8—H8 | 119.5 | N31—C31—H31E | 109.5 |
C10—C9—C8 | 118.49 (17) | C32—C31—H31E | 109.5 |
C10—C9—C12 | 121.16 (17) | N31—C31—H31D | 109.5 |
C8—C9—C12 | 120.34 (18) | C32—C31—H31D | 109.5 |
C11—C10—C9 | 121.18 (16) | H31E—C31—H31D | 108.0 |
C11—C10—H10 | 119.4 | C37—C32—C33 | 119.79 (15) |
C9—C10—H10 | 119.4 | C37—C32—C31 | 119.85 (17) |
C10—C11—C6 | 120.01 (17) | C33—C32—C31 | 120.36 (18) |
C10—C11—H11 | 120.0 | C32—C33—C34 | 119.5 (2) |
C6—C11—H11 | 120.0 | C32—C33—H33 | 120.2 |
C9—C12—H12A | 109.5 | C34—C33—H33 | 120.2 |
C9—C12—H12C | 109.5 | C35—C34—C33 | 120.3 (2) |
H12A—C12—H12C | 109.5 | C35—C34—H34 | 119.8 |
C9—C12—H12B | 109.5 | C33—C34—H34 | 119.8 |
H12A—C12—H12B | 109.5 | C34—C35—C36 | 120.61 (17) |
H12C—C12—H12B | 109.5 | C34—C35—H35 | 119.7 |
O8—C13—O7 | 121.95 (17) | C36—C35—H35 | 119.7 |
O8—C13—C14 | 124.61 (17) | C35—C36—C37 | 119.6 (2) |
O7—C13—C14 | 113.33 (15) | C35—C36—H36 | 120.2 |
C15—C14—C19 | 119.28 (17) | C37—C36—H36 | 120.2 |
C15—C14—C13 | 122.87 (16) | C32—C37—C36 | 120.2 (2) |
C19—C14—C13 | 117.77 (17) | C32—C37—H37 | 119.9 |
C16—C15—C14 | 119.86 (17) | C36—C37—H37 | 119.9 |
| | | |
C5—O5—C2—C3 | −156.6 (1) | O8—C13—C14—C15 | 177.1 (2) |
C5—O5—C2—C1 | 81.94 (15) | O7—C13—C14—C15 | −6.6 (2) |
O2—C1—C2—O5 | 5.00 (19) | O8—C13—C14—C19 | −6.3 (3) |
O1—C1—C2—O5 | −175.61 (13) | O7—C13—C14—C19 | 169.93 (16) |
O2—C1—C2—C3 | −115.88 (16) | C19—C14—C15—C16 | −2.5 (3) |
O1—C1—C2—C3 | 63.51 (17) | C13—C14—C15—C16 | 174.04 (19) |
C13—O7—C3—C2 | −151.0 (1) | C14—C15—C16—C17 | 0.9 (3) |
C13—O7—C3—C4 | 85.53 (16) | C15—C16—C17—C18 | 1.6 (3) |
O5—C2—C3—O7 | −76.5 (1) | C15—C16—C17—C20 | −178.3 (2) |
C1—C2—C3—O7 | 46.49 (16) | C16—C17—C18—C19 | −2.6 (3) |
O5—C2—C3—C4 | 47.17 (17) | C20—C17—C18—C19 | 177.3 (2) |
C1—C2—C3—C4 | 170.19 (13) | C17—C18—C19—C14 | 1.0 (3) |
O7—C3—C4—O4 | 28.5 (2) | C15—C14—C19—C18 | 1.5 (3) |
C2—C3—C4—O4 | −92.48 (17) | C13—C14—C19—C18 | −175.2 (2) |
O7—C3—C4—O3 | −152.91 (13) | N21—C21—C22—C27 | 84.8 (2) |
C2—C3—C4—O3 | 86.13 (17) | N21—C21—C22—C23 | −97.8 (2) |
C2—O5—C5—O6 | 1.2 (2) | C27—C22—C23—C24 | 0.7 (4) |
C2—O5—C5—C6 | −179.4 (1) | C21—C22—C23—C24 | −176.7 (2) |
O6—C5—C6—C7 | −177.72 (16) | C22—C23—C24—C25 | 0.7 (4) |
O5—C5—C6—C7 | 2.9 (2) | C23—C24—C25—C26 | −2.0 (5) |
O6—C5—C6—C11 | 0.4 (2) | C24—C25—C26—C27 | 1.8 (5) |
O5—C5—C6—C11 | −178.94 (14) | C23—C22—C27—C26 | −0.9 (3) |
C11—C6—C7—C8 | 1.0 (2) | C21—C22—C27—C26 | 176.5 (2) |
C5—C6—C7—C8 | 179.11 (16) | C25—C26—C27—C22 | −0.3 (4) |
C6—C7—C8—C9 | −0.4 (3) | N31—C31—C32—C37 | 87.1 (2) |
C7—C8—C9—C10 | −0.5 (3) | N31—C31—C32—C33 | −92.5 (2) |
C7—C8—C9—C12 | −179.74 (18) | C37—C32—C33—C34 | 0.5 (3) |
C8—C9—C10—C11 | 0.9 (3) | C31—C32—C33—C34 | −179.86 (19) |
C12—C9—C10—C11 | −179.87 (18) | C32—C33—C34—C35 | −0.3 (4) |
C9—C10—C11—C6 | −0.4 (3) | C33—C34—C35—C36 | 0.4 (4) |
C7—C6—C11—C10 | −0.6 (3) | C34—C35—C36—C37 | −0.6 (3) |
C5—C6—C11—C10 | −178.81 (15) | C33—C32—C37—C36 | −0.8 (3) |
C3—O7—C13—O8 | −10.3 (2) | C31—C32—C37—C36 | 179.64 (17) |
C3—O7—C13—C14 | 173.4 (1) | C35—C36—C37—C32 | 0.8 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···O41i | 0.96 (1) | 1.93 (1) | 2.875 (2) | 169 (2) |
N21—H21B···O4 | 0.95 (1) | 2.02 (1) | 2.888 (2) | 150 (2) |
N21—H21C···O1ii | 0.96 (1) | 1.72 (1) | 2.673 (2) | 172 (2) |
N31—H31A···O3i | 0.95 (1) | 1.87 (1) | 2.803 (2) | 168 (2) |
N31—H31B···O51 | 0.95 (1) | 1.93 (1) | 2.807 (2) | 153 (2) |
N31—H31C···O4 | 0.96 (1) | 1.79 (1) | 2.729 (2) | 168 (2) |
O41—H41A···O3 | 0.94 (1) | 1.88 (1) | 2.785 (2) | 160 (2) |
O41—H41B···O2ii | 0.94 (3) | 2.00 (3) | 2.931 (2) | 173 (3) |
O51—H51A···O1i | 0.94 (1) | 1.86 (1) | 2.783 (2) | 168 (2) |
O51—H51B···O2 | 0.94 (1) | 1.90 (1) | 2.804 (2) | 162 (2) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | 2C8H12N+·C20H16O82−·2CH4O·H2O | 2C7H10N+·C20H16O82−·2H2O |
Mr | 710.80 | 636.68 |
Crystal system, space group | Monoclinic, P21 | Orthorhombic, P212121 |
Temperature (K) | 113 | 113 |
a, b, c (Å) | 10.9366 (1), 8.0785 (1), 22.0995 (2) | 6.8805 (1), 19.2606 (1), 25.5545 (2) |
α, β, γ (°) | 90, 103.324 (1), 90 | 90, 90, 90 |
V (Å3) | 1899.96 (3) | 3386.55 (6) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.40 × 0.40 × 0.35 | 0.35 × 0.25 × 0.25 |
|
Data collection |
Diffractometer | Nonius Kappa CCD area-detector diffractometer | Nonius Kappa CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7708, 7708, 3969 | 28533, 4225, 3955 |
Rint | 0.009 | 0.027 |
(sin θ/λ)max (Å−1) | 0.626 | 0.643 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.095, 1.12 | 0.034, 0.084, 1.07 |
No. of reflections | 7708 | 4225 |
No. of parameters | 502 | 458 |
No. of restraints | 11 | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.26 | 0.28, −0.26 |
Selected geometric parameters (Å, º) for (I) topO1—C1 | 1.251 (3) | O7—C3 | 1.437 (2) |
O2—C1 | 1.251 (3) | C1—C2 | 1.537 (3) |
O3—C4 | 1.257 (3) | C2—C3 | 1.520 (3) |
O4—C4 | 1.240 (3) | C3—C4 | 1.547 (3) |
O5—C2 | 1.445 (2) | | |
| | | |
C5—O5—C2—C3 | −156.8 (2) | C2—O5—C5—C6 | 165.5 (2) |
C13—O7—C3—C2 | −171.0 (2) | C3—O7—C13—C14 | −178.0 (2) |
O5—C2—C3—O7 | −76.3 (2) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···O61 | 0.95 (3) | 1.80 (2) | 2.716 (3) | 158 (3) |
N21—H21B···O2i | 0.96 (1) | 1.99 (1) | 2.929 (3) | 166 (3) |
N21—H21C···O2ii | 0.95 (1) | 1.95 (2) | 2.846 (3) | 155 (3) |
N31—H31A···O3i | 0.95 (3) | 1.87 (1) | 2.795 (3) | 162 (3) |
N31—H31B···O51 | 0.96 (1) | 1.82 (1) | 2.768 (3) | 170 (3) |
N31—H31C···O1 | 0.95 (3) | 1.92 (1) | 2.843 (2) | 165 (3) |
O41—H41···O4 | 1.00 (4) | 1.82 (2) | 2.767 (3) | 158 (5) |
O51—H51···O4 | 0.99 (3) | 1.82 (2) | 2.757 (3) | 158 (3) |
O61—H61A···O3i | 0.94 (3) | 1.81 (3) | 2.750 (2) | 172 (4) |
O61—H61B···O1 | 0.944 (12) | 1.80 (2) | 2.687 (2) | 156 (4) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+1. |
Selected geometric parameters (Å, º) for (II) topO1—C1 | 1.259 (2) | O7—C3 | 1.446 (2) |
O2—C1 | 1.237 (2) | C1—C2 | 1.545 (2) |
O3—C4 | 1.253 (2) | C2—C3 | 1.516 (2) |
O4—C4 | 1.249 (2) | C3—C4 | 1.545 (2) |
O5—C2 | 1.438 (2) | | |
| | | |
C5—O5—C2—C3 | −156.6 (1) | C2—O5—C5—C6 | −179.4 (1) |
C13—O7—C3—C2 | −151.0 (1) | C3—O7—C13—C14 | 173.4 (1) |
O5—C2—C3—O7 | −76.5 (1) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N21—H21A···O41i | 0.96 (1) | 1.93 (1) | 2.875 (2) | 169 (2) |
N21—H21B···O4 | 0.95 (1) | 2.02 (1) | 2.888 (2) | 150 (2) |
N21—H21C···O1ii | 0.96 (1) | 1.72 (1) | 2.673 (2) | 172 (2) |
N31—H31A···O3i | 0.95 (1) | 1.87 (1) | 2.803 (2) | 168 (2) |
N31—H31B···O51 | 0.95 (1) | 1.93 (1) | 2.807 (2) | 153 (2) |
N31—H31C···O4 | 0.96 (1) | 1.79 (1) | 2.729 (2) | 168 (2) |
O41—H41A···O3 | 0.94 (1) | 1.88 (1) | 2.785 (2) | 160 (2) |
O41—H41B···O2ii | 0.94 (3) | 2.00 (3) | 2.931 (2) | 173 (3) |
O51—H51A···O1i | 0.94 (1) | 1.86 (1) | 2.783 (2) | 168 (2) |
O51—H51B···O2 | 0.94 (1) | 1.90 (1) | 2.804 (2) | 162 (2) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y+1/2, −z+1/2. |
This work arose from a systematic study of chiral host acids with amine guests. Previous examples of the structures derived from the host (2R,3R)-(-)-di-O-p-toluoyltartaric acid or its enantiomer with amines showed that the acid is mono-deprotonated (Liao et al. 2003; Hansen et al. 1998). Liao et al. (2003) have characterized the structure of (R)-α-{[(1,1-dimethylethyl)ammonio]methyl}-(3,5-dihydroxyphenyl)methanol (2S,3S)-di-O-toluoyltartrate monohydrate, in which the N atom on the base is protonated and one of the carboxylic acid moieties is deprotonated. The anhydrous salt of the same compound has similar features [Cambridge Structural Database (CSD; Allen, 2002), reference codes GACXUE and GACYEP01, respectively]. Hansen et al. (1998) have described the structure of (+)-(R)-3-(N,N-dimethylammonio)-1,1-diphenyl-1-butanol (-)-(2R,3R)-O,O'-di-p-toloyltartrate, in which the base is again protonated on the N atom and one carboxylic acid moiety is anionic (CSD reference code GORCAR). In contrast, the structure of (2S,5S)-1,6-diammonio-2,5-dimethyl-3,4-dithiahexane (2S,3S)-di-O-(4-toluoyl)tartrate ethanol solvate sesquihydrate (Elz et al., 1987) shows the thiahexane to be bis-protonated and the tartrate to have lost two H atoms (CSD reference code FEWLEY). We noted these features by observing the C—O bond lengths of the carboxylic acid moieties in which there was no ambiguity as to whether the carboxylic acid moiety was deprotonated or not. In addition, the corresponding amines displayed an extra H atom at N, the geometry of which was tetrahedral. We have also analysed differences in the conformations of the tartrate anions and have noted that the absolute value of the torsion angle about the central C—C bond is approximately 76° in the completely deprotonated anion, but is reduced to 61–70° in the monoprotonated species. There were no discernible patterns in the other four torsion angles in the adjacent C—O and O—C bonds of the tartrates, which are described later.
We have characterized the structures of (2R,3R)-toluoyltartaric acid, L, with (R)-(+)-1-phenylethylamine (A) and benzylamine (B) (see scheme), and present the results here. The former forms a compound with the stoichiometry L.2A·2MeOH·H2O [compound (I); Fig. 1] and the latter a compound with the stoichiometry L.2B·2H2O [compound (II); Fig. 2].
Compound (I) crystallizes in the space group P21 with Z = 2. The refinement showed that the N atoms of the amines are protonated and the carboxyl moieties of the acid exhibit similar C—O bond lengths, ranging from 1.240 (3) to 1.257 (3) Å, so they may be represented as (CO2)− moieties.
The structure is extensively hydrogen-bonded, as shown in Fig. 3. There are double ribbons of the toluoyltartrate anions running in the [010] direction, which are bridged by 1-phenylethylammonium cations and water molecules, while the methanol molecules are hydrogen bonded to the amine and the acid ions. Details of the hydrogen bonding are given in Table 2.
The conformation of the toluoyltartrate anion is governed by the torsion angles about the central C—C bond and the adjacent C—O and O—C bonds. These are reported in Table 1, together with salient bond lengths. The conformation is such that the aromatic toluoyl moieties lie approximately perpendicular to each other.
Compound (II) crystallizes in the space group P212121 with Z = 4. The toluoyltartaric acid again forms anions, with both its carboxyl moieties deprotonated, and the amines display protonated N atoms. The packing is such that the structure forms infinite sheets perpendicular to [001] and is held together by hydrogen bonds, in which the water molecules and amine cations bridge the acid anions. This is shown in Fig. 4. Details of the hydrogen bonding are given in Table 4. The conformation of the toluoyltartrate in this structure is similar to that of (I), as are the C—O bond lengths of the anionic carboxyl moiety (Table 3).
We note that the absolute values of the torsion angles about the central C—C bond of the anions in these compounds are close to that found in the dithiahexane compound elucidated by Elz et al. (1987).